A multinuclear solid state NMR, density functional theory and X-Ray diffraction study of hydrogen bonding in Group I hydrogen dibenzoates
A multinuclear solid state NMR, density functional theory and X-Ray diffraction study of hydrogen bonding in Group I hydrogen dibenzoates
复制标题
I 族二苯甲酸氢盐中氢键的多核固态 NMR、密度泛函理论和 X 射线衍射研究
作者：
Rees G
采用核磁共振晶体学方法，结合多核固态核磁共振（SSNMR）、x射线结构测定和密度泛函数理论（DFT）来表征苯甲酸（BZA）和相应的I族碱金属二苯甲酸氢（HD）体系中的氢键排列。由于XRD数据往往不能精确地确定氢键内的质子位置，因此实验SSNMR参数与测量包括平面增广波（GIPAW） DFT预测它们的能力之间的关系成为有助于进一步优化结构的强大约束。1H和13C的MAS NMR方法都通过精确测量1H和13C的各向同性化学位移以及单个13C的化学位移张量元素，提供了对氢键的初步描述；DFT计算明确地证实了这一点，它们一起准确地描述了氢键强度随单价阳离子大小变化的趋势。此外，17O MAS和DOR NMR形成了一个强大的组合来表征O环境，DOR技术提供了高分辨率的17O NMR数据，有助于明确验证传统17O MAS NMR处理的等效O位置的数量。进一步的多核MAS和静态NMR研究涉及四极性7Li， 39K， 87Rb和133c核，以及相关的DFT计算，提供了趋势和氢键几何形状的证实，有助于理解这些排列。尽管单晶x射线研究报告的每个氢键排列中的晶体学H位置容易存在不确定性，但I族碱的测量值和DFT计算的化学位移和四极张量参数之间的良好确证表明，这些报告的H位置是可靠的。
An NMR crystallographic approach incorporating multinuclear solid state NMR (SSNMR), X-ray structure determinations and density functional theory (DFT) are used to characterise the H bonding arrangements in benzoic acid (BZA) and the corresponding Group I alkali metal hydrogen dibenzoates (HD) systems. Since the XRD data often cannot precisely confirm the proton position within the hydrogen bond, the relationship between the experimental SSNMR parameters and the ability of gauge included plane augmented wave (GIPAW) DFT to predict them becomes a powerful constraint that can assist with further structure refinement. Both the 1H and 13C MAS NMR methods provide primary descriptions of the H bonding via accurate measurements of the 1H and 13C isotropic chemical shifts, and the individual 13C chemical shift tensor elements; these are unequivocally corroborated by DFT calculations, which together accurately describe the trend of the H bonding strength as the size of the monovalent cation changes. In addition, 17O MAS and DOR NMR form a powerful combination to characterise the O environments, with the DOR technique providing highly resolved 17O NMR data which helps verify unequivocally the number of inequivalent O positions for the conventional 17O MAS NMR to process. Further multinuclear MAS and static NMR studies involving the quadrupolar 7Li, 39K, 87Rb and 133Cs nuclei, and the associated DFT calculations, provide trends and a corroboration of the H bond geometry which assist in the understanding of these arrangements. Even though the crystallographic H positions in each H bonding arrangement reported from the single crystal X-ray studies are prone to uncertainty, the good corroboration between the measured and DFT calculated chemical shift and quadrupole tensor parameters for the Group I alkali species suggest that these reported H positions are reliable.
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DOI：
10.1016/j.pnmrs.2007.07.004
发表时间：
2008-02
影响因子：
6.1
作者：
Gang Wu
通讯作者：
Gang Wu
氨基硼烷钾 KNH2BH3 的第一性原理计算：结构和 39K NMR 波谱
影响因子：
3.7
作者：
K. Shimoda;A. Yamane;T. Ichikawa;Y. Kojima
通讯作者：
Y. Kojima
一些一元酸的酸盐的晶体结构。
DOI：
--
发表时间：
1954
期刊：
影响因子：
--
作者：
J. M. Skinner;G. M. Stewart;J. Speakman
通讯作者：
J. Speakman
影响因子：
15
作者：
ASAKAWA, N;KUROKI, S;OZAKI, T
通讯作者：
OZAKI, T
影响因子：
15
作者：
Gu, ZT;Ridenour, CF;McDermott, A
通讯作者：
McDermott, A